Cellulose acetate compositions containing oximes



Patentedv Feb. 28, 1-933 2 HENRY n'fsinrnfor:noc'misggmyou]; Assre von. 'ro EASTMAN KODAK com. PA,N Y,01ROC1IESTER,NEWYOBK,ACORBOBATIONDFNEW'YORK" I i r onrmunosn ACETATEfcomosIrronsoonrAmme} oxnms Nolbrawing,

"This invention relates; to; compositi s f, o

" ,ployed'to increase flexibility, transparency,f

toughness and, other properties which will, enhance thevalue of ,tlieresulting product matter in which cellulose organic esters, such as: cellulose acetate, are combined or mixed with other substances, suchas a compatible plasticizer, with or without a common solvent for both, and with orwithoutbther useful additionagents, so that, the resulting product will have properties such; as will? make the composition-highly advantageous for use in o the plastic and analogous arts,.:such, for in-, stance, as the, manufacture of wrapping sheetsor tissue, photographic film, molding compounds and products, artificial silk, varnishes .or lacquers, coating compositions and thelikep, o

One object of this invention is to produce compositions of matterxwhich may be made into permanently transparent, strong and flexible sheets or films-of ,desired gthinness which are substantially waterproof, are Bun-t affected by ordinary photographic fluids and possess: the desired properties of I a support I for sensitive .photographiccoatings. An-' other object-of myinventioni-is to produce a' composition of matter which isbapable of easy and convenient manipulation infithe plastic and analogousarts, such as in the manufacture of" sheets, films, artificial silk filaments, -;varnishes,' lacquers and: the like, and-to produce ,alcompositionwhich will not injure, or. be injured by, the substances I or surfaces withjwhich it is associated {during manufacture. "Another object of my inven-e tion is to produce compositions-Which can be molded at elevated temperatures,- ;'and high pressures to produce plastic products having the desirable properties of celluloid @Other I objectswill become apparent tothose skilled in the art to which this invention pertains;

While cellulose acetatehas loeen known for decades, ithas also been known that .to utilize it in variouspla'stic arts it: is 'necessaryltomix i I therewith such plasticizing oraconditioning agents as I triphenyl phosphate, monochlorpounds and the like.

\ 'Application 'liled February 10,1932, Ser-ialKo. 592,181;

compoundsof various kinds have been em-f- Addition products for the same or similar, purposes are also added to cellulose acetate to prepare it for use inithe other plastic artsy such as in the manufacture of lacquers,- var-1 nishes, artificial silk filaments, 'molded com While the plasticizers or other addition agents heretofore discovered havehad their utility in the art, the in-,

QFFIIACEQ I creasing use to which cellulose "acetate has beenput and the increasing number of desir ableproperties required of cellulose-acetate 1 .Ihost purposes havemade the discovery of newjand economical plasticizers or other addition agents a matter of considerable, importance to the art. This has been a problem of some difliculty, since many of the nitrocellulose solvents are not solvents for cellulose acetate,--and many substances which act astplasticizers for nitrocellulose are vnot suf-i ficiently compatiblewith cellulose acetateto "be'used as plasticizers in cellulose acetate "composltlons; 7

I I have ,di covered that valuable properties may" be; induced in and/or contributedflto compositions containing organic" derivatives of cellulose, such as cellulose acetate, byfadd-l Ling 1 thereto as plasticizing compounds c erta' n ornmes, namely acetophenone oxime,diacetyl monoxnne, cyclohe'xanone oxime, and,

furfural oxime. TheseoXimes have all been described in the literature. The particularly usefulproperties'which they induce in "or contribute to cellulosic compositions containing them are hereinafter enumerated 5111 order that thoseskilled in this art may better; understand my invention, 1 would state, by w'ayof illustration, "that for the manufacture of photographic :filmfor other sheets :my new compositions of matter'may be compounded asfollows 100 partsof ace- 1 tone soluble cellulose acetate, i. e.- cellulose acetate c'ontainingfrom-36% to 42% acetyl acetone Tothissolutionmaybeaddedfrom to about 75 parts by weight of acetophenone oxime or of diacetyl monoxime or of cyclohexanone oxime or of furfural' oxime. WVithin the limits stated, the amount ofplasticizer may be decreased or increased, depending upon whether it is desired to decrease or increase, respectively, the properties which these plasticizers contribute to the finished product. The amount of. solvent employed may also be increased or decreased,

depending upon whether it is desired to have a more or less freely flowing composition, respectively. 7 i

A composition of matter prepared as above described may be deposited upon any suitable .film-forming-surface to form a film or. sheet,

in a manner wellknown to those skilled in the art. A film so produced haspermanently brilliant transparency (even where asmuch as 50 to partsof the oxime per 100 parts of cellulose organicester, such as cellulose acetate, is used) and low infiammability, burning no more readily than ordinary newsprint. Films or sheets produced inaccordance with my invention are quite tough and flexible. For instance, films of cellulose acetate plasticized with,10%. to 7 5% (parts by 0 weight based on the cellulose acetate) of acetophenone oxime had an initial flexibil ty from 100% to 565% greater than that of film containing no plasticizer, films plasticized with 10% to 7 5%. of diacetyl monoxime had an initial flexibility from to 300% greater than that of film containing no plasticizer, a film plasticized with 15% of cyclohexanone oxime had an initial flexibility 65% greater than thatof a film. containing no plasticizer, and films containing from 10% to 20% of fu'rfural oximehad an initial fleximany years. The sum total 'ofthe above advantageous properties of pr oducts produced from my new compositionsis considerably in excess ofthat of products produced, with what have previously been regarded as the better plasticizers. 9

Other similar solvents (instead of acetone) which are compatible with the cellulose lacetate and my newplasticizers may also occur to those skilled in this art. In like manner,

these plasticizers maybe compounded with other single organic esters of cellulose, such as cellulose propionate, butyrate and the like, or with mixed organic esters, such as cellulose aceto-stearate, cellulose aceto-propionate, or cellulose aceto-malate, a suitable solvent which will dissolve both the cellulosic derivative and the plasticizer being employed.

Inasmuch as my above-described compositions of matter are useful in the production of films and sheets, it will be apparent that my new plasticizers may also be employed with advantage in the other branches of the plas tic art. .For instance, my above-described compositions of matter maybe employed in the manufacture of artificial silk by the dry spinning method. With the proper coagulating bath they may also be employed for wet spinning. Itmay be desired to employ compositions of difi'erent viscosity or evaporation characteristics, but this is a mere matterof changing the solvent proportion or adding evaporation retardent-s or other high or intermediate boiling constituents, has been well known in the art for more than a decade. My novel plasticizers may also be employed with advantage in connection with a number of the known lacquer and various formulae with which they may be found to be compatible. In such cases the plasticizer is usuallyfirst put into solution in the cellulose derivative solution, and if nonsolvents are added for the purpose of cheapening the composition they are added only to such an extent as willnot precipitate thederivative from solution. Also the plasticizeris usually employed in relatively large amounts, such as from 50 to 60 parts, in compounding lacquers. Other uses within the scope of my invention will also suggest themselves to those skilled in the art and are to be included within the scope of the claims appended hereto.

These" oximesmay also be advantageously used as plasticizersin cellulose acetate molding compositions. For instance, when about 20% or 30% (parts by wei ht based on the cellulose acetate) ofacetop enone oxime or of diacetyl monoximeqor of cyclohexanone oxime or ofiurfura l oxime is homogeneous- 'ly mixed with cellulose acetate, the mixture may be converted into a hard, translucent plasticproduct'by moldingat a temperature ofabout 140; C. and a pressure of from 2500 to 4000 pounds per square inch for a period of from 2 to 5 minutes, ina manner already known to those skilled in molding compounds of that nature. V i

What I claim as my invention and desire to c be secured by Letters Patent of the United States 1. vA composition of matter comprising an organicesterof cellulose and an oxime selected from the group consisting of acetophenone oxime, diacetyl monoxime, cyclohexanone oxime and furfural'oxime.

' 2. A composition of matter comprising cellulose acetate and an oxime selected from the group consisting of acetophenone oxime, di-

acetyl monoxime, .cyclohexanone oxime and furfuraloxime. 3. A composition lulose acetate and acetophenone oxime.

4. A composition of matter comprising cel- V .lulose acetate and diacetyl monoxime.

5. A composition of matter comprising cellulose acetate and furfural: oxime.

6. A composition of matter comprising 100 parts of cellulose acetate and about :10 to 7 5' parts, by weight, of an'oxime selected from the group consisting of acetophenone, oxime,

diacetyl monoxime, cyclohexanone oxime and furfural oxime. p l

*7. A relatively thin sheet comprising 100 parts of cellulose acetateand about 10 to 75 parts, by Weight, of an oxime selected from the group consisting of acetophenone oxime, chacetyl monoxlme, cyclohexanone oximeandr furfural oxime.

8. A molding composition adapted to molding under elevated, temperatures and high pressures, comprising cellulose acetate and an oxime selected from the group consisting' of acetophenone oxime, diacetyl monoxime, cyclohexanone oximeand 'furfural oxime. V r

Signed at Rochester, New York this 6t 1 day'of January, 1932.

HENRY B.

ofmatter comprising cel- I l 

